EP1138724B1 - Surface-treated metallic-oxide fine powder and its production and use - Google Patents
Surface-treated metallic-oxide fine powder and its production and use Download PDFInfo
- Publication number
- EP1138724B1 EP1138724B1 EP01108199A EP01108199A EP1138724B1 EP 1138724 B1 EP1138724 B1 EP 1138724B1 EP 01108199 A EP01108199 A EP 01108199A EP 01108199 A EP01108199 A EP 01108199A EP 1138724 B1 EP1138724 B1 EP 1138724B1
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- EP
- European Patent Office
- Prior art keywords
- fine powder
- oxide fine
- metallic
- silane coupling
- amino group
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/20—Powder free flowing behaviour
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Definitions
- This invention relates to a hydrophobic surface-treated metallic-oxide fine powder, which has good flow ability and excellent stability against agitation time, and especially relates to a hydrophobic surface-treated silica fine powder. More specifically, this invention relates to a hydrophobic surface-treated metallic-oxide fine powder which improves the stability against agitation time, its production method, and an electrophotographic toner using the same, regarding the hydrophobic surface-treated silica fine powder etc., which is added in a powder coating, an electrophotographic toner, etc., in order to improve the flow ability, to prevent aggregation or to adjust charge, etc.
- the surface-treated metallic-oxide fine powder in which the surface of metallic-oxide fine powder, such as silica, titania, and alumina, is treated with organic materials, is widely used as the flow ability improving agent of the electrophotographic toner for a copying machine, a laser beam printer, and a plain-paper facsimile.
- the tribo-electro static charge to an iron powder and an iron oxide powder as a carrier is one of the important quality factors.
- the metallic-oxide powder which has negative charge in the tribo-electro static charge is general, the metallic-oxide powder which is controlled to positive charge is also known.
- a metallic-oxide powder having positive charge or zero charge, which is introduced with the amino group and the hydrophobic group is disclosed in Japanese Patent Laid Open No.62-185405.
- a method is shown in Japanese Patent Laid Open No.63-52561 in which the silica synthesized by a vapor phase method is treated with silane containing epoxy groups and subsequently with amines.
- a metallic-oxide powder, which was heated with the modified silicone oil containing epoxy groups, and treated with an organic compound containing amino group is shown in Japanese Patent Laid Open No.63-155155.
- US 4,618,556 discloses a developer comprising a binder resin, a colorant and a positive charge controller which comnprise fumed silica particles treated with a coupling agent, wherein the positive charge controller has a hydrophobicity of 30 to 80 as nmeasure by the methanol titration test.
- the coupling agent a large number of possible compounds are listed having a hydrolyzable group and a non-hydrolyzable organic group bonded to a tetravalent center atom of Si or Ti.
- US 6,004,711 discloses toner compositions comprising a toner particulate including resin, a magnetic component and a charge control agent, and an extra-particulate additive comprising a first hydrophobic additive having negative tribocharging properties and a second hydrophobic additive having positive tribocharging properties.
- US 4,973,540 discloses developers comprising a resin, a colorant and inorganic fine particles having a positively chargeable polar group and a negatively chargeable polar group.
- the inorganic fine particles may be surface-treated with fluorine-coupling agent and amine coupling agents.
- the present invention solves the above-mentioned conventional problems, and provides a hydrophobic surface-treated metallic-oxide fine powder having excellent stability against agitation time as well as good flow ability
- a metallic-oxide fine powder, especially silica fine powder, which has excellent stability against agitation time is obtained.
- a surface-treated powder is obtained in which the difference between the amounts of charge for 1 minute and 5 minutes is less than 200 ⁇ C/g, or the ratio of said amounts is less than 2.5.
- the surface-treated metallic-oxide fine powder of the present invention controls the charge of the metallic-oxide fine powder and improves the stability by suppressing the variation of the amount of charge with time by surface-treating with two silane coupling agents containing an amino group, one of which is for controlling the charge and the other is for increasing the charge stability, and a hydrophobic agent and introducing plural kinds of amino groups and hydrophobic groups to the surface of the metallic-oxide fine powder.
- this invention relates to a hydrophobic surface-treated metallic-oxide fine powder which comprises the following formulations and its production method or use
- the surface-treated metallic-oxide fine powder of the present invention especially as the silica fine powder, so-called fumed silica can be used efficiently, which has a specific surface area (by nitrogen adsorption-process or BET process) of less than 400m 2 /g and was made by flame hydrolysis of a volatile silicon compound such as a silicon halide compound.
- AEROSIL50, 90G, 130, 200, 300, 380, 380S, TT600, OX50 can be used, which are the product names of NIPPON AEROSIL Co., Ltd. and are on the market.
- the surface-treated metallic-oxide fine powder of the present invention is explained, taking a silica fine powder as an example.
- alumina powder and titanium oxide powder can be explained in the same way.
- the surface-treated silica powder of this invention stabilizes the tribo-electro static charge by surface-treating, using the silane coupling agent containing the primary amino group shown by the following formula 3, and at least one of the silane coupling agents containing an amino group chosen from the silane coupling agents containing the amino group shown by the formula 4, and a hydrophobic agent.
- X is a functional group which can be hydrolyzed
- R is a hydrogen group or an alkyl group
- a part of R1 and R2 can be replaced by nitrogen, oxygen or sulfur atom.
- n is an integer from 1 to 3
- m is an integer from 1 to 6.
- the hydrolysis groups represented by X are specifically a chloro group, an alkoxy group, an acetoxy group, a hydroxy group, etc.
- the silane coupling agent containing a primary amino group shown by the above formula 3 mainly controls the charge and the following compounds are mentioned as specific examples.
- ⁇ -amino propyltrimethoxysilane, or ⁇ -amino propyltriethoxy-silane is preferable from the point of reactivity and kinds of sub-products, it is not limited to these compounds.
- silane coupling agent containing an amino group shown by above formula 4 mainly improves the charge stability, and although the following compounds are mentioned as specific examples, it is not limited to these compounds.
- the addition amount of the silane coupling agent containing a primary amino group of formula 3 is adjusted according to the specific surface area of the silica fine powder, 0.1 - 20 weight part is generally desirable to 100 weight part of the silica fine powder. Moreover, with respect to the addition amount of the silane coupling agent of formula 4, 0.1 to 20 weight part is desirable to 100 weight part of the silica fine powder.
- these amounts are under 0.1 weight parts, the controlling of the charge of the silica fine powder is not sufficient since there are few amounts of amino group introduced onto the surface of the silica fine powder, and good stability of the charge cannot be obtained.
- the amounts are more than 20 weight part, the silica fine powder itself becomes to show hydrophilicity since the amino group is a hydrophilic functional group, and thus the hydrophobicity required as a toner additive cannot be obtained.
- any materials of the following can be used if they are general ones: alkyl silazane compounds such as hexamethyldisilazane, alkylalkoxy-silane compounds such as dimethylmethoxy-silane, dimethylethoxy-silane, trimethylmethoxy-silane methyltrimethoxy-silane, and butyltrimethoxy-silane, chlorosilane compounds such as dimethyldichloro-silane and trimethylchlorosilane, a silicone varnish containing reactive functional groups, a non-reactive silicone varnish, a silicone oil containing reactive functional group, a non-reactive silicone oil, etc.
- alkyl silazane compounds such as hexamethyldisilazane
- alkylalkoxy-silane compounds such as dimethylmethoxy-silane, dimethylethoxy-silane, trimethylmethoxy-silane methyltrimethoxy-silane, and butyltri
- the viscosity is less than 1000 cst. If the viscosity is 1000 cst or more, it is difficult to apply the surface-treated agent uniformly on the silica fine powder, and an aggregation of the silica fine powder may occur to give a bad influence on the tribo-electro static charge of the silica fine powder.
- hydrophobic agents are not limited specifically if they are general ones.
- hexamethyldisilazane or dimethylsiloxane is desirable in order to obtain high hydrophobicity.
- the addition amount of the hydrophobic agent is adjusted according to the specific surface area of the silica fine powder and the addition amount of the silane coupling agent containing amino group, the amount of 5 - 50 weight part of silane coupling agent containing amino group is desirable in general. If this amount is less than 5 weight part, high hydrophobicity cannot be obtained, on the other hand, even if the amount is more than 50 weight part, hydrophobicity is practically equal and the aggregation may rather increase, so that it is not desirable.
- the silica fine powder is charged into a container having a stirring equipment represented by a Henschel mixer etc., and is stirred under nitrogen atmosphere.
- the silane coupling agent containing a primary amino group of the general formula 3, the silane coupling agent containing an amino group of the general formula 4, and the hydrophobic agent, are added to the stirred powder to be mixed uniformly, or these surface-treated agents are sprayed to the silica powder to be mixed uniformly.
- the addition order of the silane coupling agents of formula 3 and formula 4 is not limited
- these surface-treated agents and silica powder After mixing these surface-treated agents and silica powder uniformly, they are heated for more than 30 minutes at a temperature of less than 300°C.
- the heating temperature is 300°C or higher, it is not desirable since the amino group introduced for controlling charge is heat decomposed, and it may cause a poor tribo-electro static charge and a coloring of the silica fine powder itself, etc.
- the hydrophobic surface-treated silica powder can be obtained, which improves the charge control and stability.
- a hydrophobic silica powder can be obtained wherein the tribo-electro static charge to iron powders satisfies at least one of the relational expressions shown in the following formula 1 or 2:
- silica powder synthesized by a vapor phase method (NIHON AEROSIL product; Aerosil 200) of 200 m 2 /g by BET specific surface area
- a mixed solution comprising 5g of ⁇ - aminopropyltriethoxy-silane (Shin-Etsu Chemical Co., Ltd. product: KBE 903) , N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxy-silane (Shin-Etsu Chemical Co., Ltd. product: KBM603), and 15g of a dimethyl-silicone oil (Shin-Etsu Chemical Co., Ltd. product: KF 96) was sprayed to 100g of said silica powder. The sprayed powder was heated while being stirred for 60 minutes at 200°C, and then cooled to prepare the surface-treated silica fine powder A.
- Each mixed solution which consists of the silica powder synthesized by a vapor phase method having the specific surface areas shown in Table 1, the silane coupling agent containing primary amino group shown by the formula 3, the silane coupling agent containing amino group shown by the formula 4, and the hydrophobic agent, was used to prepare the surface-treated silica fine powders B to G by the same process as in Example 1 under the heating conditions shown in Table 1.
- Each mixed solution consisting of the silica powder synthesized by a vapor phase method having the specific surface areas shown in Table 1, the silane coupling agent containing amino group shown by either of formula 3 or 4, and the hydrophobic agent, was used to be prepared the surface-treated silica fine powders H to J by the same process as in Example 1 under the heating conditions shown in Table 1.
- metallic-oxide fine powders such as silica with a small charge variation with time are provided.
- the powder such as silica has a small charge variation with time, and is suitable as an additive of powder coatings or an electrophotographic toner.
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Description
This invention relates to a hydrophobic surface-treated metallic-oxide fine
powder, which has good flow ability and excellent stability against agitation
time, and especially relates to a hydrophobic surface-treated silica fine powder. More
specifically, this invention relates to a hydrophobic surface-treated metallic-oxide fine
powder which improves the stability against agitation time, its production
method, and an electrophotographic toner using the same, regarding the
hydrophobic surface-treated silica fine powder etc., which is added in a powder coating, an
electrophotographic toner, etc., in order to improve the flow ability, to
prevent aggregation or to adjust charge, etc.
The surface-treated metallic-oxide fine powder, in which the surface
of metallic-oxide fine powder, such as silica, titania, and alumina, is treated
with organic materials, is widely used as the flow ability improving agent of
the electrophotographic toner for a copying machine, a laser beam printer,
and a plain-paper facsimile. In such applications, the tribo-electro static
charge to an iron powder and an iron oxide powder as a carrier is one of the
important quality factors. Wherein, although the metallic-oxide powder
which has negative charge in the tribo-electro static charge is general, the
metallic-oxide powder which is controlled to positive charge is also known.
In the charge of the metallic-oxide fine powder, for example, a
metallic-oxide powder having positive charge or zero charge, which is
introduced with the amino group and the hydrophobic group, is disclosed in
Japanese Patent Laid Open No.62-185405. In addition, a method is shown
in Japanese Patent Laid Open No.63-52561 in which the silica synthesized
by a vapor phase method is treated with silane containing epoxy groups
and subsequently with amines. Moreover, a metallic-oxide powder,
which was heated with the modified silicone oil containing epoxy groups, and
treated with an organic compound containing amino group, is shown in
Japanese Patent Laid Open No.63-155155.
US 4,618,556 discloses a developer comprising a binder resin,
a colorant and a positive charge controller which comnprise
fumed silica particles treated with a coupling agent, wherein
the positive charge controller has a hydrophobicity of 30 to
80 as nmeasure by the methanol titration test. As the
coupling agent a large number of possible compounds are
listed having a hydrolyzable group and a non-hydrolyzable
organic group bonded to a tetravalent center atom of Si or
Ti.
US 6,004,711 discloses toner compositions comprising a toner
particulate including resin, a magnetic component and a
charge control agent, and an extra-particulate additive
comprising a first hydrophobic additive having negative
tribocharging properties and a second hydrophobic additive
having positive tribocharging properties.
US 4,973,540 discloses developers comprising a resin, a
colorant and inorganic fine particles having a positively
chargeable polar group and a negatively chargeable polar
group. The inorganic fine particles may be surface-treated
with fluorine-coupling agent and amine coupling agents.
However, while these conventional metallic-oxide powders, especially
silica powder, can control early time tribo-electro static charge, the stability
with time is inferior. That is, there is a problem that the charge varies
much as agitation time becomes longer. As a method for solving this
problem, addition of titanium oxide to the toner is proposed in Japanese
Patent Laid Open No.8-220791. Moreover, a method of adding alumina to
the toner is proposed in Japanese Patent Application No. 9-150382 (Japanese Patent
Laid Open No. 10-326028). However, compared with silica powder, titanium-oxide
powder and alumina powder are inferior in the effectiveness for improving the toner
flow ability.
The present invention solves the above-mentioned conventional
problems, and provides a hydrophobic surface-treated metallic-oxide fine powder
having excellent stability against agitation time as well as good flow ability
According to this invention, a metallic-oxide fine powder, especially silica
fine powder, which has excellent stability against agitation time is obtained.
For example, a surface-treated powder is obtained in which the difference
between the amounts of charge for 1 minute and 5 minutes is less than 200
µC/g, or the ratio of said amounts is less than 2.5.
The surface-treated metallic-oxide fine powder of the present
invention controls the charge of the metallic-oxide fine powder and improves
the stability by suppressing the variation of the amount of charge with time
by surface-treating with two silane coupling agents containing an amino group,
one of which is for controlling the charge and the other is for increasing the
charge stability, and a hydrophobic agent and introducing plural kinds of
amino groups and hydrophobic groups to the surface of the metallic-oxide
fine powder.
That is, this invention relates to a hydrophobic surface-treated metallic-oxide
fine powder which comprises the following formulations and its production
method or use
wherein the tribo-electro static charge is stabilized by surface-treating of the metallic-oxide fine powder, using a silane coupling agent containing a primary amino group shown by the following formula 3, and at least one of silane coupling agent containing amino group chosen from silane coupling agents containing amino group shown by the following formula 4, and a hydrophobic agent:
Hereafter, this invention is concretely explained based on example.
As the surface-treated metallic-oxide fine powder of the present
invention, especially as the silica fine powder, so-called fumed silica can be
used efficiently, which has a specific surface area (by nitrogen adsorption-process
or BET process) of less than 400m2/g and was made by flame
hydrolysis of a volatile silicon compound such as a silicon halide compound.
For example, as such kind of silica powder, AEROSIL50, 90G, 130, 200, 300,
380, 380S, TT600, OX50 can be used, which are the product names of
NIPPON AEROSIL Co., Ltd. and are on the market.
Hereafter, the surface-treated metallic-oxide fine powder of the
present invention is explained, taking a silica fine powder as an example.
In addition, alumina powder and titanium oxide powder can be explained in
the same way.
The surface-treated silica powder of this invention stabilizes the
tribo-electro static charge by surface-treating, using the silane coupling
agent containing the primary amino group shown by the following formula 3,
and at least one of the silane coupling agents containing an amino group chosen
from the silane coupling agents containing the amino group shown by the
formula 4, and a hydrophobic agent.
XnR(3-n) Si - (CH2 ) m-NH2
XnR(3-n) Si - (CH2 ) m-NR1R2
Here, X is a functional group which can be hydrolyzed, R is a hydrogen
group or an alkyl group, and R1 and R2 are a hydrogen group, an alkyl
group, or an aryl group except for the case of R1=R2=H. In addition, a part
of R1 and R2 can be replaced by nitrogen, oxygen or sulfur atom. n is an
integer from 1 to 3, and m is an integer from 1 to 6. The hydrolysis groups
represented by X, are specifically a chloro group, an alkoxy group, an acetoxy
group, a hydroxy group, etc.
The silane coupling agent containing a primary amino group shown by
the above formula 3 mainly controls the charge and the following compounds
are mentioned as specific examples. Although γ-amino propyltrimethoxysilane,
or γ-amino propyltriethoxy-silane is preferable from the point of
reactivity and kinds of sub-products, it is not limited to these compounds.
(MeO)3SiCH2CH2CH2NH2
(EtO)3SiCH2CH2CH2NH2
(i-PrO)3SiCH2CH2CH2NH2
(EtO)3SiCH2NH2
Cl3SiCH2CH2CH2NH2
(MeO)2MeSiCH2CH2CH2NH2
(EtO)2MeSiCH2CH2CH2NH2
(MeO)3SiCH2CH2CH2NH2
(EtO)3SiCH2CH2CH2NH2
(i-PrO)3SiCH2CH2CH2NH2
(EtO)3SiCH2NH2
Cl3SiCH2CH2CH2NH2
(MeO)2MeSiCH2CH2CH2NH2
(EtO)2MeSiCH2CH2CH2NH2
The above-mentioned silane coupling agent containing an amino group
shown by above formula 4 mainly improves the charge stability, and
although the following compounds are mentioned as specific examples, it is
not limited to these compounds.
(MeO)3SiCH2CH2CH2NHEt
(MeO)3SiCH2CH2CH2NHBu
(MeO)3SiCH2CH2CH2NEt2
(MeO)3SiCH2CH2CH2NBu2
(MeO)3SiCH2CH2CH2NHCH2CH2NH2
(EtO)3SiCH2CH2CH2NHCH2CH2NH2
(MeO)3SiCH2CH2CH2NHC6H5
(MeO)2MeSiCH2CH2CH2NHCH2CH2NH2
Cl3SiCH2CH2CH2NHEt
(AcO)3SiCH2CH2CH2NHEt
(AcO)2MeSiCH2CH2CH2NHCH2CH2NH2
(MeO)3SiCH2CH2CH2NHCH2CH2OMe
(MeO)3SiCH2CH2CH2NHEt
(MeO)3SiCH2CH2CH2NHBu
(MeO)3SiCH2CH2CH2NEt2
(MeO)3SiCH2CH2CH2NBu2
(MeO)3SiCH2CH2CH2NHCH2CH2NH2
(EtO)3SiCH2CH2CH2NHCH2CH2NH2
(MeO)3SiCH2CH2CH2NHC6H5
(MeO)2MeSiCH2CH2CH2NHCH2CH2NH2
Cl3SiCH2CH2CH2NHEt
(AcO)3SiCH2CH2CH2NHEt
(AcO)2MeSiCH2CH2CH2NHCH2CH2NH2
(MeO)3SiCH2CH2CH2NHCH2CH2OMe
Although the addition amount of the silane coupling agent
containing a primary amino group of formula 3 is adjusted according to the
specific surface area of the silica fine powder, 0.1 - 20 weight part is generally
desirable to 100 weight part of the silica fine powder. Moreover, with
respect to the addition amount of the silane coupling agent of formula 4, 0.1
to 20 weight part is desirable to 100 weight part of the silica fine powder.
When these amounts are under 0.1 weight parts, the controlling of the
charge of the silica fine powder is not sufficient since there are few amounts
of amino group introduced onto the surface of the silica fine powder, and good
stability of the charge cannot be obtained. On the other hand, when the
amounts are more than 20 weight part, the silica fine powder itself becomes
to show hydrophilicity since the amino group is a hydrophilic functional
group, and thus the hydrophobicity required as a toner additive cannot be
obtained.
As the hydrophobic agent used for this invention, any materials of
the following can be used if they are general ones: alkyl silazane
compounds such as hexamethyldisilazane, alkylalkoxy-silane compounds
such as dimethylmethoxy-silane, dimethylethoxy-silane, trimethylmethoxy-silane
methyltrimethoxy-silane, and butyltrimethoxy-silane, chlorosilane
compounds such as dimethyldichloro-silane and trimethylchlorosilane,
a silicone varnish containing reactive functional groups, a non-reactive
silicone varnish, a silicone oil containing reactive functional group,
a non-reactive silicone oil, etc. In addition, in order to obtain high
hydrophobicity, it is desirable to use hexamethyldisilazane or a silicone oil.
Moreover, in the case of the silicone oil, it is desirable that the viscosity is
less than 1000 cst. If the viscosity is 1000 cst or more, it is difficult to apply
the surface-treated agent uniformly on the silica fine powder, and
an aggregation of the silica fine powder may occur to give a bad influence on
the tribo-electro static charge of the silica fine powder.
The above-mentioned hydrophobic agents are not limited specifically
if they are general ones. In addition, hexamethyldisilazane or
dimethylsiloxane is desirable in order to obtain high hydrophobicity.
Although the addition amount of the hydrophobic agent is adjusted
according to the specific surface area of the silica fine powder and the
addition amount of the silane coupling agent containing amino group, the
amount of 5 - 50 weight part of silane coupling agent containing amino group
is desirable in general. If this amount is less than 5 weight part, high
hydrophobicity cannot be obtained, on the other hand, even if the amount is
more than 50 weight part, hydrophobicity is practically equal and the
aggregation may rather increase, so that it is not desirable.
It is possible to use a general method to treat the silica fine powder
by these surface-treated agents. Specifically, the silica fine powder is
charged into a container having a stirring equipment represented by a
Henschel mixer etc., and is stirred under nitrogen atmosphere. The silane
coupling agent containing a primary amino group of the general formula 3, the
silane coupling agent containing an amino group of the general formula 4, and
the hydrophobic agent, are added to the stirred powder to be mixed
uniformly, or these surface-treated agents are sprayed to the silica powder to
be mixed uniformly. The addition order of the silane coupling agents of
formula 3 and formula 4 is not limited
After mixing these surface-treated agents and silica powder
uniformly, they are heated for more than 30 minutes at a temperature of less
than 300°C. When the heating temperature is 300°C or higher, it is not
desirable since the amino group introduced for controlling charge is heat
decomposed, and it may cause a poor tribo-electro static charge and a
coloring of the silica fine powder itself, etc.
With the above-mentioned surface-treatment, the hydrophobic
surface-treated silica powder can be obtained, which improves the charge
control and stability. Specifically, a hydrophobic silica powder can be obtained wherein
the tribo-electro static charge to iron powders satisfies at least one of the
relational expressions shown in the following formula 1 or 2:
|Q1-Q5| < 200 µC/g
Q1/Q5 < 2.5
wherein Q1 is the tribo-electro static charge of the agitation of the iron and
the fine silica powders at 1 minute after, and Q5 is the tribo-electro static
charge at 5 minutes after. Since the variation of the tribo-electro static
charge with time is small, the surface-treated metallic-oxide fine powder of
this invention is suitable for an additive of powder coatings or an
electrophotographic toner.
Hereafter, this invention is illustrated by examples.
While the silica powder synthesized by a vapor phase method
(NIHON AEROSIL product; Aerosil 200) of 200 m2/g by BET specific surface
area, was put into a reaction vessel and stirred under nitrogen atmosphere,
a mixed solution comprising 5g of γ - aminopropyltriethoxy-silane (Shin-Etsu
Chemical Co., Ltd. product: KBE 903) , N-(β-aminoethyl)-γ-aminopropyltrimethoxy-silane
(Shin-Etsu Chemical Co., Ltd. product:
KBM603), and 15g of a dimethyl-silicone oil (Shin-Etsu Chemical Co., Ltd.
product: KF 96) was sprayed to 100g of said silica powder. The sprayed
powder was heated while being stirred for 60 minutes at 200°C, and then
cooled to prepare the surface-treated silica fine powder A.
Each mixed solution, which consists of the silica powder synthesized
by a vapor phase method having the specific surface areas shown in Table 1,
the silane coupling agent containing primary amino group shown by the
formula 3, the silane coupling agent containing amino group shown by the
formula 4, and the hydrophobic agent, was used to prepare the surface-treated
silica fine powders B to G by the same process as in Example 1 under
the heating conditions shown in Table 1.
Each mixed solution, consisting of the silica powder synthesized by
a vapor phase method having the specific surface areas shown in Table 1, the
silane coupling agent containing amino group shown by either of formula 3
or 4, and the hydrophobic agent, was used to be prepared the surface-treated
silica fine powders H to J by the same process as in Example 1 under the
heating conditions shown in Table 1.
0.1g of this surface-treated silica powder and 50g of iron powder were
put into a glass-vessel to be mixed, and after agitation for a predetermined
time (1 minute and 5 minutes) by a Turbula Mixer, 0.1g of this mixed powder
was extracted. The tribo-electro static charge was measured after the
nitrogen blowing was performed for 1 minute by the blow-off charge
measuring apparatus (TOSHIBA CHEMICAL Co., LTD. product: TB-200).
The result is shown in Table 2. As shown in Table 2, in each silica powder A
to G of the present invention, |Q1 - Q5|, which is the difference of the
charges within 5 minutes after the mixing with iron powder, is less than 200
µC/g, or the ratio of the charge Q1/Q5 is less than 2.5. On the other hand,
in the silica powder H of the comparative example, the ratio of the charge is
large although the difference of the charge is small, that is, the stability of
the charge with time is inferior. Moreover, in the silica powder I of the
comparative example, although the difference of the charges is not so large,
the ratio of the charge is large. In the silica powder J of the comparative
example, the difference of the charge is extremely large.
According to the present invention, metallic-oxide fine powders such
as silica with a small charge variation with time are provided. The
powder such as silica has a small charge variation with time, and is
suitable as an additive of powder coatings or an electrophotographic
toner.
Claims (7)
- A hydrophobic surface-treated metallic-oxide fine powder satisfying at least one of the relational expressions of the following formula 1 or 2, in which the amount of tribo-electro static charge to iron powders is shown:
wherein the tribo-electro static charge is stabilized by surface-treating the metallic-oxide fine powder, using a silane coupling agent containing a primary amino group shown by following formula 3, at least one of silane coupling agents containing amino group, chosen from the silane coupling agents containing amino group shown by following formula 4, and a hydrophobic agent: - A surface-treated metallic-oxide fine powder according to claim 1, wherein said powder has a tribo-electro static charge which satisfies at least one of the relational expressions shown by above-mentioned formula 1 or 2, by surface-treating said metallic-oxide fine powder, using the silane coupling agent containing a primary amino group shown by above mentioned formula 3, at least one of silane coupling agents containing amino groups chosen from silane coupling agents containing amino groups shown by above-mentioned formula 4, and a hydrophobic agent .
- A surface-treated metallic-oxide fine powder according to claim 1 or 2, wherein the addition of a silane coupling agent containing primary amino group of above-mentioned formula 3 is from 0.1 to 20 % by weight, the addition of the silane coupling agent containing amino group of above-mentioned formula 4 is from 0.1 to 20 % by weight, and the addition of a hydrophobic agent is from 5 to 50 % by weight.
- A surface-treated metallic-oxide fine powder according to claim 1, 2, or 3,
wherein, the hydrophobic agent is an alkyl silazane compound, an alkyl alkoxy silane compound, a chloro-silane compound, a silicone varnish containing reactive functional groups, a non-reactive silicone varnish, a silicone oil containing reactive functional groups, or a non-reactive silicone oil, and the degree of hydrohobicity by a permeability method is 70% or more. - A surface-treated metallic-oxide fine powder according to any one of claims 1 to 4, wherein, said metallic-oxide fine powder is a silica fine powder which is generated by the flame hydrolysis of a volatile silicon compound and is less than 400m2/g by BET specific surface area.
- A production method of a surface-treated metallic-oxide fine powder according to claim 1,
wherein a silane coupling agent containing primary amino group shown by above-mentioned formula 3, a silane coupling agent containing amino group shown by above-mentioned formula 4, and a hydrophobic agent, are sprayed to the metallic-oxide fine powder and heated, or said metallic-oxide fine powder is heated after having been dipped in a mixed solution of these agents. - A toner containing a surface-treated silica fine powder according to any one of claims 1 to 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000098466 | 2000-03-31 | ||
| JP2000098466A JP4512872B2 (en) | 2000-03-31 | 2000-03-31 | Surface-modified silica fine powder and method for producing the same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1138724A2 EP1138724A2 (en) | 2001-10-04 |
| EP1138724A3 EP1138724A3 (en) | 2002-07-31 |
| EP1138724B1 true EP1138724B1 (en) | 2005-12-28 |
Family
ID=18612943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01108199A Expired - Lifetime EP1138724B1 (en) | 2000-03-31 | 2001-03-30 | Surface-treated metallic-oxide fine powder and its production and use |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6573018B2 (en) |
| EP (1) | EP1138724B1 (en) |
| JP (1) | JP4512872B2 (en) |
| DE (1) | DE60116171T2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8029761B2 (en) | 2006-09-01 | 2011-10-04 | Cabot Corporation | Surface-treated metal oxide particles |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001021529A1 (en) * | 1999-09-22 | 2001-03-29 | Nippon Aerosil Co., Ltd. | Surface modified fine silica powder and use thereof |
| US6677095B2 (en) | 1999-12-08 | 2004-01-13 | Nippon Aerosil Co., Ltd. | Fine metal oxide powder having high dispersibility and toner composition comprising the same |
| DE10151478C1 (en) † | 2001-10-18 | 2003-03-13 | Wacker Chemie Gmbh | Production of aminoalkylsilyl-modified solid, used in powder system, as thickener or in toner, developer or charge transfer ancillary, involves reacting surface hydroxyl groups with cyclic silazane |
| WO2004060803A1 (en) * | 2002-12-27 | 2004-07-22 | Nippon Aerosil Co., Ltd. | Highly dispersible, fine, hydrophobic silica powder and process for producing the same |
| JP4442896B2 (en) * | 2005-03-10 | 2010-03-31 | 株式会社リコー | Non-magnetic one-component developer |
| US7250080B1 (en) | 2006-09-06 | 2007-07-31 | Tronox Llc | Process for the manufacture of organosilicon compound-treated pigments |
| US20080053336A1 (en) * | 2006-09-06 | 2008-03-06 | Tronox Llc | Aqueous coating compositions with improved tint strength and gloss properties, comprising pigments surface-treated with certain organosilicon compounds |
| US20080070146A1 (en) | 2006-09-15 | 2008-03-20 | Cabot Corporation | Hydrophobic-treated metal oxide |
| US8202502B2 (en) | 2006-09-15 | 2012-06-19 | Cabot Corporation | Method of preparing hydrophobic silica |
| US8435474B2 (en) * | 2006-09-15 | 2013-05-07 | Cabot Corporation | Surface-treated metal oxide particles |
| US8455165B2 (en) * | 2006-09-15 | 2013-06-04 | Cabot Corporation | Cyclic-treated metal oxide |
| DE102007033448A1 (en) * | 2007-07-18 | 2009-01-22 | Wacker Chemie Ag | Highly dispersed metal oxides with a high positive surface charge |
| DE112010002932B4 (en) | 2009-07-14 | 2017-06-14 | Nippon Aerosil Co., Ltd. | Surface-modified metal oxide powder and process for producing the same |
| US9284643B2 (en) * | 2010-03-23 | 2016-03-15 | Pneumaticoat Technologies Llc | Semi-continuous vapor deposition process for the manufacture of coated particles |
| JP5668465B2 (en) * | 2010-12-24 | 2015-02-12 | 日本ゼオン株式会社 | Toner for electrostatic image development |
| US9298113B2 (en) * | 2013-01-16 | 2016-03-29 | Ricoh Company, Ltd. | Electrophotographic photoconductor, image forming apparatus, and process cartridge |
| KR102323121B1 (en) * | 2014-07-28 | 2021-11-05 | 덴카 주식회사 | Spherical alumina powder and resin composition including same |
| JP6645020B2 (en) * | 2015-03-25 | 2020-02-12 | 富士ゼロックス株式会社 | Thermosetting powder coatings, painted products, and methods for producing painted products |
| KR101849453B1 (en) | 2016-04-26 | 2018-04-17 | 한국세라믹기술원 | Prepartion of hydrophobid inorganic materials using vapor phase floating method |
| US20190241719A1 (en) * | 2016-10-12 | 2019-08-08 | Wacker Chemie Ag | Hydrophobing additives |
| KR101872868B1 (en) * | 2017-03-07 | 2018-07-02 | (주)윈스 | A conductivity ceramic composition having high performance electric conductivity |
| CN106964771B (en) * | 2017-05-16 | 2018-09-14 | 合肥学院 | A kind of characterizing method of the control method of superfine Mg powder oxygen content, oxidation resistance |
| CN108059168B (en) * | 2018-01-19 | 2019-09-24 | 四川广阳环保科技有限公司 | A kind of method, product and purposes preparing improved silica adsorbent using chlorosilane raffinate |
| CN107970880B (en) * | 2018-01-19 | 2019-09-03 | 四川广阳环保科技有限公司 | A kind of preparation method of improved silica adsorbent |
| CN114836057B (en) * | 2022-04-07 | 2023-06-09 | 福建远翔新材料股份有限公司 | Preparation method of nano hydrated silicon dioxide through superhydrophobic modification |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58185405A (en) | 1982-04-26 | 1983-10-29 | Nippon Aerojiru Kk | Fine powder of surface-modified metal oxide |
| JPS58216252A (en) * | 1982-06-11 | 1983-12-15 | Nippon Aerojiru Kk | Dry type toner |
| GB2128764B (en) * | 1982-08-23 | 1986-02-19 | Canon Kk | Electrostatographic developer |
| JPH0619583B2 (en) | 1985-08-31 | 1994-03-16 | 三田工業株式会社 | Toner for electrophotography |
| JPS63155155A (en) | 1986-12-19 | 1988-06-28 | Konica Corp | Electrostatic developer and electrostatic developing method and image forming method |
| JPH01237561A (en) * | 1987-10-13 | 1989-09-22 | Canon Inc | Developer for developing electrostatic latent image |
| JP2636304B2 (en) * | 1988-03-03 | 1997-07-30 | コニカ株式会社 | Image forming method |
| US4973540A (en) * | 1988-08-31 | 1990-11-27 | Minolta Camera Kabushiki Kaisha | Developer for electrostatic latent image containing fine particle comprising positively and negatively chargeable polar group |
| JPH0380261A (en) * | 1989-08-24 | 1991-04-05 | Canon Inc | Production of toner for developing electrostatic charge image |
| JP3318997B2 (en) * | 1993-02-03 | 2002-08-26 | 三菱マテリアル株式会社 | Hydrophobic silica powder, its production method and developer for electrophotography |
| JP3697283B2 (en) | 1995-02-14 | 2005-09-21 | コニカミノルタビジネステクノロジーズ株式会社 | Toner for electrostatic image development |
| JP3150645B2 (en) | 1997-05-23 | 2001-03-26 | 株式会社巴川製紙所 | Electrostatic toner |
| DE69940446D1 (en) * | 1998-05-11 | 2009-04-02 | Nippon Aerosil Co Ltd | Process for the preparation of fine hydrophobic metal oxide powders for electrophotography |
| JP4186254B2 (en) * | 1998-05-11 | 2008-11-26 | 日本アエロジル株式会社 | Method for producing surface-modified metal oxide fine powder and method for producing electrophotographic toner composition |
| US6004711A (en) * | 1999-02-03 | 1999-12-21 | Lexmark International, Inc. | Toner composition including positive and negative tribocharging hydrophobic extra-particulate additives |
-
2000
- 2000-03-31 JP JP2000098466A patent/JP4512872B2/en not_active Expired - Lifetime
-
2001
- 2001-03-29 US US09/821,622 patent/US6573018B2/en not_active Expired - Fee Related
- 2001-03-30 DE DE60116171T patent/DE60116171T2/en not_active Expired - Fee Related
- 2001-03-30 EP EP01108199A patent/EP1138724B1/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8029761B2 (en) | 2006-09-01 | 2011-10-04 | Cabot Corporation | Surface-treated metal oxide particles |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1138724A2 (en) | 2001-10-04 |
| DE60116171T2 (en) | 2006-09-21 |
| JP2001281914A (en) | 2001-10-10 |
| EP1138724A3 (en) | 2002-07-31 |
| JP4512872B2 (en) | 2010-07-28 |
| US20020004026A1 (en) | 2002-01-10 |
| US6573018B2 (en) | 2003-06-03 |
| DE60116171D1 (en) | 2006-02-02 |
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